EP3733282A1 - Hydrocarbon adsorbent - Google Patents

Hydrocarbon adsorbent Download PDF

Info

Publication number
EP3733282A1
EP3733282A1 EP18896734.3A EP18896734A EP3733282A1 EP 3733282 A1 EP3733282 A1 EP 3733282A1 EP 18896734 A EP18896734 A EP 18896734A EP 3733282 A1 EP3733282 A1 EP 3733282A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
zeolite
zsm
copper
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18896734.3A
Other languages
German (de)
French (fr)
Other versions
EP3733282A4 (en
Inventor
Chun Yong Kang
Chang Hwan Kim
Jungkyu Choi
Eun-Hee Jang
Jin Seong Kim
La Young CHOI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hyundai Motor Co
Korea University Research and Business Foundation
Kia Corp
Original Assignee
Hyundai Motor Co
Kia Motors Corp
Korea University Research and Business Foundation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hyundai Motor Co, Kia Motors Corp, Korea University Research and Business Foundation filed Critical Hyundai Motor Co
Publication of EP3733282A1 publication Critical patent/EP3733282A1/en
Publication of EP3733282A4 publication Critical patent/EP3733282A4/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
    • B01D53/9486—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start for storing hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B01J20/2809—Monomodal or narrow distribution, uniform pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3221—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond the chemical bond being an ionic interaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/723—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
    • F01N3/0835—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/311—Porosity, e.g. pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a hydrocarbon adsorbent with improved hydrocarbon adsorption capacity.
  • HC hydrocarbons
  • PM partate matter
  • the HC is mostly oxidized by three-way catalysts (TWCs), and the three-way catalysts are activated at a temperature of about 200 to 300 °C or higher, and thus, in a cold-start section in which the three-way catalysts are not activated, HC corresponding to 50 to 80 % of a total HC emission is emitted.
  • TWCs three-way catalysts
  • HC trap hydrocarbon adsorbent
  • the hydrocarbon adsorbent is a device that adsorbs HC emitted in the cold-start section and desorbs the HC when the three-way catalyst becomes activated at a temperature of 200 to 300 °C.
  • hydrocarbon adsorbent As a hydrocarbon adsorbent, zeolite having high physical and chemical stability has been extensively studied. Performance of the hydrocarbon adsorbent is tested by measuring adsorption/desorption of propene and toluene, which are typical HC emission materials. Studies on the performance of the hydrocarbon adsorbent according to a zeolite structure, a Si/Al ratio, and whether or not metal impregnation is performed, have been conducted.
  • the present invention has been made in an effort to provide a hydrocarbon adsorbent with improved hydrocarbon adsorption capacity.
  • a hydrocarbon adsorbent includes a ZSM-5 zeolite containing copper, and an Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40, and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite.
  • All the wt % of the content of the copper herein are based on the total weight of the ZSM-5 zeolite.
  • a content of the copper may be 3 wt% to 7 wt% based on the total weight of the ZSM-5 zeolite.
  • efficiency of the hydrocarbon adsorbent may be 55 % or greater.
  • efficiency of the hydrocarbon adsorbent may be 60 % or greater.
  • efficiency of the hydrocarbon adsorbent may be 70 % or greater.
  • the hydrocarbon may include a hydrocarbon having 5 or more carbon atoms.
  • a hydrocarbon adsorbent includes a beta zeolite containing copper, a Si/Al molar ratio of the beta zeolite may be 12.5 to 19, and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the beta zeolite.
  • a content of the copper may be 3 wt% to 10 wt% based on the total weight of the beta zeolite.
  • a hydrocarbon eliminating system includes: trapping hydrocarbon by using ZSM-5 zeolite or beta zeolite containing copper at a temperature of 150 °C or less; desorbing the trapped hydrocarbon at a temperature of 150 °C or greater; and oxidizing the desorbed hydrocarbon.
  • a Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40 and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite or the beta zeolite, and a Si/Al molar ratio of the beta zeolite may be 12.5 to 19 and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite or the beta zeolite.
  • the present invention provides a hydrocarbon adsorbent with improved hydrocarbon adsorption capacity.
  • a hydrocarbon adsorbent includes a ZSM-5 zeolite containing copper, a Si/Al molar ratio of the ZSM-5 zeolite is 11.5 to 40, and a content of the copper is 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite. All the wt % of the content of the copper herein are based on the total weight of the ZSM-5 zeolite.
  • adsorption performance especially adsorption performance at a high temperature, may be improved by controlling the Si/Al ratio and the content of the supported Cu of the zeolite, and it is possible to rapidly deoxidize and simultaneously desorb hydrocarbon through a combination of a transition metal oxide and a hydrocarbon trap.
  • FIG. 1 illustrates a configuration of purifying exhaust gas of a gasoline vehicle with a three-way catalyst.
  • exhaust gas of a gasoline vehicle is purified by a three-way catalyst, and when a temperature of the catalyst is 400 °C or greater, the catalyst has purification performance of about 100 %.
  • the three-way catalyst may not be normally operated, thus the exhaust gas is not purified and is discharged into the atmosphere. Particularly, it is known that about 70 % of the hydrocarbons are discharged in the cold-start section.
  • the hydrocarbons discharged in the cold-start section are adsorbed by the hydrocarbon adsorbent, and then, when the hydrocarbon is desorbed from the hydrocarbon adsorbent at the end of the warm-up of the three-way catalyst, it may be purified through the three-way catalyst.
  • FIG. 2 illustrates a configuration in which a hydrocarbon adsorbent adsorbs and desorbs hydrocarbon.
  • the hydrocarbon since a desorption time of hydrocarbon is delayed in an adsorbent supporting copper, compared to an adsorbent not supporting copper, the hydrocarbon may be oxidized and purified simultaneously with desorption.
  • FIG. 3 illustrates a hydrocarbon eliminating system according to an exemplary embodiment of the present invention.
  • an exemplary embodiment of the present invention includes trapping hydrocarbon by using ZSM-5 zeolite containing copper ions and copper oxide at a temperature of 150 °C or less, desorbing the trapped hydrocarbon at a temperature of 150 °C or greater, and oxidizing the desorbed hydrocarbon.
  • a Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40, and a content of copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite. Remarkable hydrocarbon trapping properties are obtained in the above range.
  • Cu was impregnated into H-type ZSM-5 particles by using a wet impregnation method. Specifically, copper nitrate trihydrate (Cu(NO 3 ) 2 ⁇ 3H 2 O, 98 %, Sigma-Aldrich) is dissolved in deionized water to prepare a solution of 0.04 M copper II nitrate (Cu(NO 3 ) 2 ). The H-type ZSM-5 particles were added to the copper nitrate solution so that 5 wt% of Cu based on the total weight of the ZSM-5 zeolite was finally impregnated.
  • Cu(NO 3 ) 2 ⁇ 3H 2 O, 98 %, Sigma-Aldrich copper nitrate trihydrate
  • Cu(NO 3 ) 2 copper II nitrate
  • the mixture was placed in a rotary evaporator, and after eliminating all moisture, the Cu-impregnated ZSM-5 was recovered to be dried at a temperature of 100 °C for about 6 hours or more, and it was calcined at a temperature of 550 °C for 6 hours at a heating rate of 1 °C/min under an air flow of 300 mL/min.
  • Example 1 A manufacturing process according to Example 1 is shown in FIG. 4 .
  • Example 2 After 60 mg of Cu/ZSM-5 zeolite respectively prepared in Example 1 was pre-treated for 30 minutes at a temperature of 600 °C under He flow in a reaction tube, it was adsorbed for 5 minutes at a temperature of 70 °C in C 3 H 6 , C 7 H 8 , CO, H2, O 2 , CO 2 , H 2 O, a carrier Ar/He mixed gas (Lambda 1 condition mixed gas) under C 3 H 6 , C 7 H 8 , O2, carrier gas Ar/He mixed gas flow for 5 minutes, and then the adsorption/desorption performance was evaluated while raising a temperature at a heating rate of 53 °C/min.
  • a carrier Ar/He mixed gas Libda 1 condition mixed gas
  • FIG. 6 illustrates process conditions of pre-treatment, adsorption, and desorption.
  • FIG. 7 illustrates process conditions and a reaction flowchart of an adsorption/desorption evaluation test.
  • Evaluation Example 2 Adsorption performance evaluation according to carbon atoms of hydrocarbon
  • Adsorption performance for C 3 H 6 and adsorption performance for C 7 H 8 were measured in the same manner as in Evaluation Example 1 for ZSM-5 zeolites having different Si/Al contents shown in FIG. 8 and FIG. 9 .
  • the Si/Al ratio of ZSM-5 affects the hydrocarbon adsorption performance. Particularly, it was confirmed that an improvement effect was remarkable in hydrocarbon (C 7 H 8 ) having large carbon atoms. According to the results of Evaluation Example 2, the smaller the Si/Al ratio, the better the hydrocarbon adsorption amount and the high temperature adsorption performance, which is determined to be due to an increase in the Br ⁇ nsted acid site.
  • Adsorption performance for C 3 H 6 and adsorption performance for C 7 H 8 were measured in the same manner as in Evaluation Example 1 for ZSM-5 zeolites supporting Cu of different contents shown in FIG. 10 and FIG. 11 .
  • Adsorption and purification performance of each sample prepared in Example 1 and shown in FIG. 4 were measured and shown in FIG. 12 and FIG. 13 .
  • the efficiency means an amount (%) of hydrocarbon that was not discharged compared to an amount of hydrocarbon provided up to a temperature of 300 °C.
  • the amount of hydrocarbon was calculated as a value when converted to CH4. (For example, calculated as C 3 H 6 ⁇ 3CH 4 , C 7 H 8 ⁇ 7CH 4 )
  • efficiency is 90 % in a case in which an amount of hydrocarbon discharged is 10.
  • a preferred copper content for obtaining efficiency of 50 % or greater was 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite, and a preferred copper content for obtaining efficiency of 80 % or greater was 1 wt% to 3 wt% based on the total weight of the ZSM-5 zeolite.
  • the hydrocarbon adsorbent suppressed the hydrocarbon emission by 55 % or greater.
  • the Si/Al molar ratio was 11.5 to 40 and the copper content was 3 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite
  • the hydrocarbon adsorbent suppressed the hydrocarbon emission by 55 % or greater.
  • the Si/Al molar ratio was 25 to 40 and the copper content was 5 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite, the hydrocarbon adsorbent suppressed the hydrocarbon emission by 60 % or greater.
  • the hydrocarbon adsorbent suppressed the hydrocarbon emission by 70 % or greater.
  • Evaluation Example 5 is similar to Evaluation Example 4, beta zeolite was used instead of ZSM-5 as the zeolite, the Si/Al molar ratio was varied from 12.5 to 150, and the same experiment as in Evaluation Example 4 was performed while changing the Cu content from 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Nanotechnology (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

A hydrocarbon adsorbent, according to one embodiment of the present invention, comprises a copper-containing ZSM-5 zeolite, wherein a Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40, and the amount of the copper included is 1 wt% to 10 wt%.

Description

    TECHNICAL FIELD Cross-reference to related application(s)
  • This application claims priority to and the benefit of Korean Patent Application No. 10-2017-0183959 filed in the Korean Intellectual Property Office on December 29, 2017, and International Patent Application No. PCT/KR2018/016590 filed in the World Intellectual Property Organization on December 24, 2018, the entire contents of which are incorporated herein by reference.
  • The present invention relates to a hydrocarbon adsorbent with improved hydrocarbon adsorption capacity.
    • BACKGROUND
  • As interest in air pollution increases, regulations for vehicle exhaust gasses such as CO, NOx, HC (hydrocarbons), and PM (particulate matter) in places such as the United States and Europe are being strengthened. Among them, the HC is mostly oxidized by three-way catalysts (TWCs), and the three-way catalysts are activated at a temperature of about 200 to 300 °C or higher, and thus, in a cold-start section in which the three-way catalysts are not activated, HC corresponding to 50 to 80 % of a total HC emission is emitted. In order to reduce the HC emission, studies on a hydrocarbon adsorbent (HC trap) have been conducted. The hydrocarbon adsorbent is a device that adsorbs HC emitted in the cold-start section and desorbs the HC when the three-way catalyst becomes activated at a temperature of 200 to 300 °C.
  • As a hydrocarbon adsorbent, zeolite having high physical and chemical stability has been extensively studied. Performance of the hydrocarbon adsorbent is tested by measuring adsorption/desorption of propene and toluene, which are typical HC emission materials. Studies on the performance of the hydrocarbon adsorbent according to a zeolite structure, a Si/Al ratio, and whether or not metal impregnation is performed, have been conducted.
    • SUMMARY OF THE INVENTION Technical Problem
  • The present invention has been made in an effort to provide a hydrocarbon adsorbent with improved hydrocarbon adsorption capacity.
    • Technical Solution
  • In order to solve the problem, a hydrocarbon adsorbent according to an exemplary embodiment of the present includes a ZSM-5 zeolite containing copper, and an Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40, and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite.
  • All the wt % of the content of the copper herein are based on the total weight of the ZSM-5 zeolite.
  • A content of the copper may be 3 wt% to 7 wt% based on the total weight of the ZSM-5 zeolite.
  • When the Si/Al molar ratio is 11.5 to 40 and the content of the copper is 3 wt% to 10 wt%, efficiency of the hydrocarbon adsorbent may be 55 % or greater.
  • When the Si/Al molar ratio is 25 to 40 and the content of the copper is 5 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite, efficiency of the hydrocarbon adsorbent may be 60 % or greater.
  • When the Si/Al molar ratio is 15 to 25 and the content of the copper is 3 wt% to 5 wt% based on the total weight of the ZSM-5 zeolite, efficiency of the hydrocarbon adsorbent may be 70 % or greater.
  • The hydrocarbon may include a hydrocarbon having 5 or more carbon atoms.
  • A hydrocarbon adsorbent according another exemplary embodiment includes a beta zeolite containing copper, a Si/Al molar ratio of the beta zeolite may be 12.5 to 19, and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the beta zeolite.
  • A content of the copper may be 3 wt% to 10 wt% based on the total weight of the beta zeolite.
  • A hydrocarbon eliminating system according to another exemplary embodiment of the present invention includes: trapping hydrocarbon by using ZSM-5 zeolite or beta zeolite containing copper at a temperature of 150 °C or less; desorbing the trapped hydrocarbon at a temperature of 150 °C or greater; and oxidizing the desorbed hydrocarbon. A Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40 and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite or the beta zeolite, and a Si/Al molar ratio of the beta zeolite may be 12.5 to 19 and a content of the copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite or the beta zeolite.
    • Advantageous Effects
  • As described above, the present invention provides a hydrocarbon adsorbent with improved hydrocarbon adsorption capacity.
    • BRIEF DESCRIPTION OF THE DRAWINGS
    • FIG. 1 illustrates a configuration of purifying exhaust gas of a gasoline vehicle with a three-way catalyst.
    • FIG. 2 illustrates a configuration in which a hydrocarbon adsorbent adsorbs and desorbs hydrocarbon.
    • FIG. 3 illustrates a hydrocarbon eliminating system according to an exemplary embodiment of the present invention.
    • FIG. 4 illustrates a manufacturing process according to Example 1.
    • FIG. 5 illustrates an image of a sample manufactured in Example 1.
    • FIG. 6 illustrates a process condition of pre-treatment, adsorption, and desorption in Evaluation Example 1.
    • FIG. 7 illustrates a process condition and a reaction flowchart of an adsorption/desorption evaluation test in Evaluation Example 1.
    • FIG. 8 illustrates a result of measuring adsorption performance of C3H6 in Evaluation Example 2.
    • FIG. 9 illustrates a result of measuring adsorption performance of C7H8 in Evaluation Example 2.
    • FIG. 10 illustrates a result of measuring adsorption performance of C3H6 in Evaluation Example 3.
    • FIG. 11 illustrates a result of measuring adsorption performance of C7H8 in Evaluation Example 4.
    • FIG. 12 and FIG. 13 illustrate a result of measuring adsorption and purification performance of a sample manufactured in Example 1.
    • FIG. 14 illustrates a result of measuring adsorption performance in Evaluation Example 5.
    DETAILED DESCRIPTION
  • The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which an exemplary embodiment of the invention is shown. As those skilled in the art would realize, the described embodiment may be modified in various different ways, all without departing from the spirit or scope of the present invention.
  • A hydrocarbon adsorbent according to an exemplary embodiment of the present invention will now be described in detail with reference to the drawings.
  • A hydrocarbon adsorbent according to an exemplary embodiment of the present invention includes a ZSM-5 zeolite containing copper, a Si/Al molar ratio of the ZSM-5 zeolite is 11.5 to 40, and a content of the copper is 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite. All the wt % of the content of the copper herein are based on the total weight of the ZSM-5 zeolite.
  • Depending on the molar ratio and the content of the supported copper, it is possible to provide a hydrocarbon adsorbent with significantly improved hydrocarbon adsorption capacity.
  • That is, according to the present invention, adsorption performance, especially adsorption performance at a high temperature, may be improved by controlling the Si/Al ratio and the content of the supported Cu of the zeolite, and it is possible to rapidly deoxidize and simultaneously desorb hydrocarbon through a combination of a transition metal oxide and a hydrocarbon trap.
  • FIG. 1 illustrates a configuration of purifying exhaust gas of a gasoline vehicle with a three-way catalyst. Referring to FIG. 1, exhaust gas of a gasoline vehicle is purified by a three-way catalyst, and when a temperature of the catalyst is 400 °C or greater, the catalyst has purification performance of about 100 %. However, in a cold-start section immediately after an engine starts, the three-way catalyst may not be normally operated, thus the exhaust gas is not purified and is discharged into the atmosphere. Particularly, it is known that about 70 % of the hydrocarbons are discharged in the cold-start section.
  • However, in this exemplary embodiment, since the zeolite-based hydrocarbon adsorbent is introduced into the exhaust gas system, until a warm-up operation of the three-way catalyst is completed, the hydrocarbons discharged in the cold-start section are adsorbed by the hydrocarbon adsorbent, and then, when the hydrocarbon is desorbed from the hydrocarbon adsorbent at the end of the warm-up of the three-way catalyst, it may be purified through the three-way catalyst.
  • FIG. 2 illustrates a configuration in which a hydrocarbon adsorbent adsorbs and desorbs hydrocarbon. Referring to FIG. 2, since a desorption time of hydrocarbon is delayed in an adsorbent supporting copper, compared to an adsorbent not supporting copper, the hydrocarbon may be oxidized and purified simultaneously with desorption.
  • FIG. 3 illustrates a hydrocarbon eliminating system according to an exemplary embodiment of the present invention. Referring to FIG. 3, an exemplary embodiment of the present invention includes trapping hydrocarbon by using ZSM-5 zeolite containing copper ions and copper oxide at a temperature of 150 °C or less, desorbing the trapped hydrocarbon at a temperature of 150 °C or greater, and oxidizing the desorbed hydrocarbon.
  • In this case, a Si/Al molar ratio of the ZSM-5 zeolite may be 11.5 to 40, and a content of copper may be 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite. Remarkable hydrocarbon trapping properties are obtained in the above range.
  • Hereinafter, a hydrocarbon adsorbent according to an exemplary embodiment of the present invention will be described through specific examples.
    • Example 1 Cu/ZSM5 zeolite synthesis
  • Cu was impregnated into H-type ZSM-5 particles by using a wet impregnation method. Specifically, copper nitrate trihydrate (Cu(NO3)2·3H2O, 98 %, Sigma-Aldrich) is dissolved in deionized water to prepare a solution of 0.04 M copper II nitrate (Cu(NO3)2). The H-type ZSM-5 particles were added to the copper nitrate solution so that 5 wt% of Cu based on the total weight of the ZSM-5 zeolite was finally impregnated. Then, the mixture was placed in a rotary evaporator, and after eliminating all moisture, the Cu-impregnated ZSM-5 was recovered to be dried at a temperature of 100 °C for about 6 hours or more, and it was calcined at a temperature of 550 °C for 6 hours at a heating rate of 1 °C/min under an air flow of 300 mL/min.
  • A manufacturing process according to Example 1 is shown in FIG. 4.
  • After the content of Cu and the Si/Al molar ratio were differently prepared according to the manufacturing method of Example 1, samples prepared with each content were as shown in FIG. 5.
    • Evaluation Example 1: HC trap adsorption/desorption performance evaluation test in cold-start section
  • After 60 mg of Cu/ZSM-5 zeolite respectively prepared in Example 1 was pre-treated for 30 minutes at a temperature of 600 °C under He flow in a reaction tube, it was adsorbed for 5 minutes at a temperature of 70 °C in C3H6, C7H8, CO, H2, O2, CO2, H2O, a carrier Ar/He mixed gas (Lambda 1 condition mixed gas) under C3H6, C7H8, O2, carrier gas Ar/He mixed gas flow for 5 minutes, and then the adsorption/desorption performance was evaluated while raising a temperature at a heating rate of 53 °C/min.
  • FIG. 6 illustrates process conditions of pre-treatment, adsorption, and desorption. FIG. 7 illustrates process conditions and a reaction flowchart of an adsorption/desorption evaluation test.
    • Evaluation Example 2: Adsorption performance evaluation according to carbon atoms of hydrocarbon
  • Adsorption performance for C3H6 and adsorption performance for C7H8 were measured in the same manner as in Evaluation Example 1 for ZSM-5 zeolites having different Si/Al contents shown in FIG. 8 and FIG. 9.
  • As a result, it was confirmed that the Si/Al ratio of ZSM-5 affects the hydrocarbon adsorption performance. Particularly, it was confirmed that an improvement effect was remarkable in hydrocarbon (C7H8) having large carbon atoms. According to the results of Evaluation Example 2, the smaller the Si/Al ratio, the better the hydrocarbon adsorption amount and the high temperature adsorption performance, which is determined to be due to an increase in the Brønsted acid site.
    • Evaluation Example 3: Adsorption and purification performance evaluation of HC trap according to supported Cu
  • Adsorption performance for C3H6 and adsorption performance for C7H8 were measured in the same manner as in Evaluation Example 1 for ZSM-5 zeolites supporting Cu of different contents shown in FIG. 10 and FIG. 11.
  • As a result, it was confirmed that in the hydrocarbon adsorption performance of ZSM-5 supporting Cu, the larger the Cu supporting content, the higher the high temperature adsorption performance and the adsorption amount of C3H6. This is a result of ion exchange of a portion of the supported Cu, resulting in an increase in the Lewis acid site. In addition, it was confirmed that CuO, which does not participate in the ion exchange and is dispersed on an outer wall of the ZSM-5, contributed to fast hydrocarbon oxidation reaction during hydrocarbon desorption.
    • Evaluation Example 4: Adsorption and purification performance of HC trap according to supported Cu and Si/Al molar ratio
  • Adsorption and purification performance of each sample prepared in Example 1 and shown in FIG. 4 were measured and shown in FIG. 12 and FIG. 13.
  • As a result, it was confirmed that the hydrocarbon adsorption and purification performance was significantly improved by the Si/Al molar ratio and supported Cu.
  • It was confirmed that a preferred Si/Al molar ratio for obtaining efficiency of 50 % or greater was 11.5 to 40, and a preferred Si/Al molar ratio for obtaining efficiency of 80 % or greater was 11.5 to 25.
  • In the present experiment, the efficiency means an amount (%) of hydrocarbon that was not discharged compared to an amount of hydrocarbon provided up to a temperature of 300 °C. The amount of hydrocarbon was calculated as a value when converted to CH4. (For example, calculated as C3H6 → 3CH4, C7H8 → 7CH4)
  • For example, when an amount of hydrocarbon provided is 100, efficiency is 90 % in a case in which an amount of hydrocarbon discharged is 10.
  • In addition, it was confirmed that a preferred copper content for obtaining efficiency of 50 % or greater was 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite, and a preferred copper content for obtaining efficiency of 80 % or greater was 1 wt% to 3 wt% based on the total weight of the ZSM-5 zeolite.
  • More specifically, when the Si/Al molar ratio was 11.5 to 40 and the copper content was 3 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite, the hydrocarbon adsorbent suppressed the hydrocarbon emission by 55 % or greater. In addition, when the Si/Al molar ratio was 25 to 40 and the copper content was 5 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite, the hydrocarbon adsorbent suppressed the hydrocarbon emission by 60 % or greater.
  • Similarly, when the Si/Al molar ratio was 15 to 25 and the copper content was 3 wt% to 5 wt%, the hydrocarbon adsorbent suppressed the hydrocarbon emission by 70 % or greater.
    • Evaluation Example 5: Comparison with Cu/Beta zeolite
  • Although Evaluation Example 5 is similar to Evaluation Example 4, beta zeolite was used instead of ZSM-5 as the zeolite, the Si/Al molar ratio was varied from 12.5 to 150, and the same experiment as in Evaluation Example 4 was performed while changing the Cu content from 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite.
  • The results are shown in FIG. 14.
  • As a result, when the Si/Al molar ratio was 12.5 to 19 and the copper content was 1 wt% to 10 wt%, it was confirmed that remarkable efficiency was obtained.
  • While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims (9)

  1. A hydrocarbon adsorbent comprising
    a ZSM-5 zeolite containing copper,
    wherein a Si/Al molar ratio of the ZSM-5 zeolite is 11.5 to 40, and
    a content of the copper is 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite.
  2. The hydrocarbon adsorbent of claim 1, wherein
    a content of the copper is 3 wt% to 7 wt% based on the total weight of the ZSM-5 zeolite.
  3. The hydrocarbon adsorbent of claim 1, wherein,
    when the Si/Al molar ratio is 11.5 to 40 and
    the content of copper is 3 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite,
    efficiency of the hydrocarbon adsorbent is 55 % or greater.
  4. The hydrocarbon adsorbent of claim 1, wherein
    the Si/Al molar ratio is 25 to 40 and
    the content of the copper is 5 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite,
    efficiency of the hydrocarbon adsorbent is 60 % or greater.
  5. The hydrocarbon adsorbent of claim 1, wherein,
    when the Si/Al molar ratio is 15 to 25 and
    the content of the copper is 3 wt% to 5 wt% based on the total weight of the ZSM-5 zeolite,
    efficiency of the hydrocarbon adsorbent is 70 % or greater.
  6. The hydrocarbon adsorbent of claim 1, wherein
    the hydrocarbon includes a hydrocarbon having 5 or more carbon atoms.
  7. A hydrocarbon adsorbent comprising
    a beta zeolite containing copper,
    wherein a Si/Al molar ratio of the beta zeolite is 12.5 to 19, and
    a content of the copper is 1 wt% to 10 wt% based on the total weight of the beta zeolite.
  8. The hydrocarbon adsorbent of claim 7, wherein
    a content of the copper is 3 wt% to 10 wt% based on the total weight of the beta zeolite.
  9. A hydrocarbon eliminating system comprising:
    trapping hydrocarbons by using ZSM-5 zeolite or beta zeolite containing copper at a temperature of 150 °C or less;
    desorbing the trapped hydrocarbon at a temperature of 150 °C or greater; and
    oxidizing the desorbed hydrocarbon,
    wherein an Si/Al molar ratio of the ZSM-5 zeolite is 11.5 to 40 and a content of the copper is 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite or the beta zeolite, or
    a Si/Al molar ratio of the beta zeolite is 12.5 to 19 and a content of the copper is 1 wt% to 10 wt% based on the total weight of the ZSM-5 zeolite or the beta zeolite.
EP18896734.3A 2017-12-29 2018-12-28 HYDROCARBON ADSORBANT Withdrawn EP3733282A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020170183959A KR102085652B1 (en) 2017-12-29 2017-12-29 Hydrocarbon Trap Comprising Metal-impregnated Zeolite Particles Having Regular Mesopores and Method of Preparing the Same
PCT/KR2018/016590 WO2019132482A1 (en) 2017-12-29 2018-12-24 Hydrocarbon adsorbent with metal-impregnated zeolite particle having regular mesopore and manufacturing method therefor
PCT/KR2018/016905 WO2019132611A1 (en) 2017-12-29 2018-12-28 Hydrocarbon adsorbent

Publications (2)

Publication Number Publication Date
EP3733282A1 true EP3733282A1 (en) 2020-11-04
EP3733282A4 EP3733282A4 (en) 2021-11-03

Family

ID=67067909

Family Applications (3)

Application Number Title Priority Date Filing Date
EP18893856.7A Withdrawn EP3733280A4 (en) 2017-12-29 2018-12-24 HYDROCARBON ADSORBANT WITH A METAL-IMPREGNATED ZEOLITE PARTICLE HAVING A REGULAR MESOPORE AND ITS MANUFACTURING PROCESS
EP18895622.1A Pending EP3733281A4 (en) 2017-12-29 2018-12-28 HYDROCARBON REMOVAL SYSTEM
EP18896734.3A Withdrawn EP3733282A4 (en) 2017-12-29 2018-12-28 HYDROCARBON ADSORBANT

Family Applications Before (2)

Application Number Title Priority Date Filing Date
EP18893856.7A Withdrawn EP3733280A4 (en) 2017-12-29 2018-12-24 HYDROCARBON ADSORBANT WITH A METAL-IMPREGNATED ZEOLITE PARTICLE HAVING A REGULAR MESOPORE AND ITS MANUFACTURING PROCESS
EP18895622.1A Pending EP3733281A4 (en) 2017-12-29 2018-12-28 HYDROCARBON REMOVAL SYSTEM

Country Status (6)

Country Link
US (5) US20200360891A1 (en)
EP (3) EP3733280A4 (en)
JP (3) JP7217278B2 (en)
KR (1) KR102085652B1 (en)
CN (3) CN111542388A (en)
WO (3) WO2019132482A1 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2581776B (en) * 2019-02-19 2022-08-17 Jaguar Land Rover Ltd Catalytic converter core having first and second regions with different thermal inertia
JP7540167B2 (en) * 2020-03-10 2024-08-27 東ソー株式会社 Hydrophobic MFI zeolite, its production method, and its uses
WO2021201018A1 (en) * 2020-03-31 2021-10-07 東ソー株式会社 Hydrocarbon adsorbent and hydrocarbon adsorption method
JPWO2022085753A1 (en) * 2020-10-23 2022-04-28
KR20220067569A (en) * 2020-11-16 2022-05-25 현대자동차주식회사 Catalyst for adsorbing hydrocarbon and hydrocarbon trap comprising the same
KR102509811B1 (en) * 2020-11-24 2023-03-14 고려대학교 산학협력단 Hydrocarbon adsorption and desorption complex comprising gas-adsorption-part and reinforcement-part and preparation method thereof
KR102529419B1 (en) * 2020-11-24 2023-05-08 고려대학교 산학협력단 Hydrocarbon adsorption and desorption complex comprising zeolite with controlled cation ratio and preparation method thereof
KR102529420B1 (en) * 2020-11-24 2023-05-08 고려대학교 산학협력단 Hydrocarbon adsorption and desorption complex comprising zeolite with controlled cation and preparation method thereof
KR20240068833A (en) * 2022-11-08 2024-05-20 현대자동차주식회사 Method for preparing a hydrocarbon adsorption catalyst, a hydrocarbon adsorption catalyst prepared thereby, and a hydrocarbon trap comprising the same
CN115770612A (en) * 2022-12-06 2023-03-10 中国科学院青岛生物能源与过程研究所 Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof
CN115920589B (en) * 2022-12-21 2023-08-11 可迪尔空气技术（北京）有限公司 Treatment method of low-concentration sewage pool waste gas

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3895080A (en) * 1972-06-06 1975-07-15 Sun Research Development Separation of cyclic compounds by adsorption on partially sorbed metallic zeolites
US3929669A (en) * 1972-12-22 1975-12-30 Universal Oil Prod Co Method for manufacturing an adsorbent useful for olefin separation
US4297328A (en) * 1979-09-28 1981-10-27 Union Carbide Corporation Three-way catalytic process for gaseous streams
JPS59196745A (en) * 1983-03-31 1984-11-08 Res Assoc Residual Oil Process<Rarop> Iron-containing zeolite composition
US5185305A (en) * 1991-11-08 1993-02-09 Ford Motor Company Catalyst system for treating the exhaust from a lean-burn gasoline-fueled engine
JP3616112B2 (en) * 1992-12-28 2005-02-02 日産自動車株式会社 Hydrocarbon adsorbent
JP3207577B2 (en) * 1993-01-20 2001-09-10 三菱重工業株式会社 Hydrocarbon adsorbent and adsorption purification method
JP3190780B2 (en) * 1994-03-17 2001-07-23 出光興産株式会社 Hydrocarbon adsorption catalyst for exhaust gas purification
JPH0810613A (en) * 1994-07-05 1996-01-16 Ngk Insulators Ltd Adsorbing material for purifying exhaust gas of car
JPH0975721A (en) * 1995-09-12 1997-03-25 Tokyo Gas Co Ltd Adsorbent for removing trace components in hydrocarbon gas and removal method
EP0768111A1 (en) * 1995-10-16 1997-04-16 Corning Incorporated Method of modifying a hydrocarbon adsorber and its use
KR100490511B1 (en) * 1996-05-29 2005-08-04 엑손모빌 케미칼 패턴츠 인코포레이티드 Zeolite catalyst and its use in hydrocarbon conversion
JP3918305B2 (en) * 1997-07-02 2007-05-23 東ソー株式会社 Hydrocarbon adsorbent and exhaust gas purification catalyst
DE69826768T2 (en) * 1997-07-02 2006-03-09 Tosoh Corp., Shinnanyo Adsorbent for hydrocarbon and catalyst for exhaust gas purification
JP3417309B2 (en) * 1997-10-28 2003-06-16 トヨタ自動車株式会社 Hydrocarbon adsorbent
WO2000066263A1 (en) * 1999-05-05 2000-11-09 Exxon Chemical Patents Inc. Zeolite bound catalyst containing at least three different zeolites; use for hydrocarbon conversion
FR2863909B1 (en) * 2003-12-22 2006-05-26 Ceca Sa PROCESS FOR PURIFYING GASEOUS STREAMS CONTAMINATED BY CO2 AND HYDROCARBON (S) AND / OR NITROGEN OXIDE (S) BY AGGLOMERIC ZEOLITIC ADSORBENT
WO2007080288A1 (en) * 2005-12-22 2007-07-19 Institut Francais Du Petrole Irregularly shaped, non-spherical supported catalyst and process for hydroconversion of heavy petroleum fractions
DE102005061713B4 (en) * 2005-12-22 2015-05-21 Süd-Chemie Ip Gmbh & Co. Kg Volatile hydrocarbon adsorber unit, method of making a zeolitic adsorbent material and zeolitic adsorbent material obtainable by the method
FR2895283B1 (en) * 2005-12-22 2008-02-01 Inst Francais Du Petrole CATALYST COMPRISING EUO ZEOLITHE, 10MR ZEOLITE AND 12MR ZEOLITE AND ITS USE IN ISOMERIZATION OF AROMATIC C8 COMPOUNDS
JP4956112B2 (en) 2006-09-22 2012-06-20 三菱自動車工業株式会社 Method for preparing HC trap catalyst
US8413433B2 (en) * 2008-07-17 2013-04-09 Ford Global Technologies, Llc Hydrocarbon retaining and purging system
KR101062666B1 (en) * 2009-02-02 2011-09-06 한국과학기술원 Palladium-supported mesoporous zeolite
US8147588B2 (en) * 2009-10-06 2012-04-03 Basf Corporation Lower reactivity adsorbent and higher oxygenate capacity for removal of oxygenates from olefin streams
CN102946998A (en) * 2010-04-08 2013-02-27 巴斯夫欧洲公司 Cu-CHA/Fe-MFI hybrid zeolite catalyst and method of using same for treating NOx in gas streams
JP2011240273A (en) 2010-05-19 2011-12-01 Jx Nippon Oil & Energy Corp Adsorbent, its production method and fuel desulfurization method
MX343465B (en) * 2010-05-21 2016-11-07 Pq Corp Novel metal - containing zeolite beta for nox reduction.
GB201100595D0 (en) * 2010-06-02 2011-03-02 Johnson Matthey Plc Filtration improvements
KR101147669B1 (en) * 2010-07-05 2012-05-21 한국과학기술원 Zeolite materials and their analogue materials comprising regularly or randomly arranged mesopore , and producing method thereof
KR101451902B1 (en) * 2012-11-26 2014-10-22 한국과학기술원 Zeolite with MRE structure and their analogue materials possessing mesopore, and synthesis method thereof
DK3016741T3 (en) * 2013-07-05 2020-07-27 Univ Danmarks Tekniske Process for the production of zeolites and zeotypes
JP6398448B2 (en) * 2013-08-30 2018-10-03 東ソー株式会社 Pentasil-type zeolite and method for producing the same
US9463447B2 (en) * 2014-01-29 2016-10-11 Ford Global Technologies, Llc Hydrocarbon trap with increased zeolite loading and improved adsorption capacity
JP6294127B2 (en) * 2014-03-31 2018-03-14 株式会社キャタラー SCR catalyst and exhaust gas purification catalyst system
BR112018015547A2 (en) * 2016-02-19 2018-12-26 Exxonmobil Res & Eng Co small crystal emm-30 zeolites, high surface area, their synthesis and use
US10105691B2 (en) * 2016-03-31 2018-10-23 Ford Global Technologies, Llc Multiple zeolite hydrocarbon traps
BR112018072009A2 (en) * 2016-04-26 2019-02-12 Basf Corporation exhaust gas treatment system and method for reducing carbon monoxide present in an exhaust gas stream

Also Published As

Publication number Publication date
JP2021509635A (en) 2021-04-01
US20200391178A1 (en) 2020-12-17
EP3733280A4 (en) 2021-10-27
EP3733281A1 (en) 2020-11-04
WO2019132612A1 (en) 2019-07-04
EP3733282A4 (en) 2021-11-03
WO2019132611A8 (en) 2019-08-01
JP2021509086A (en) 2021-03-18
CN111526941A (en) 2020-08-11
EP3733281A4 (en) 2021-08-25
CN111655367A (en) 2020-09-11
WO2019132482A1 (en) 2019-07-04
US20230191362A1 (en) 2023-06-22
CN111542388A (en) 2020-08-14
JP7217278B2 (en) 2023-02-02
KR20190081424A (en) 2019-07-09
US20210370219A1 (en) 2021-12-02
JP2021509087A (en) 2021-03-18
EP3733280A1 (en) 2020-11-04
US20200324268A1 (en) 2020-10-15
US20200360891A1 (en) 2020-11-19
KR102085652B1 (en) 2020-03-06
WO2019132611A1 (en) 2019-07-04

Similar Documents

Publication Publication Date Title
US20200324268A1 (en) Hydrocarbon adsorbent
Chen et al. Low temperature NO storage of zeolite supported Pd for low temperature diesel engine emission control
Mihai et al. The effect of Si/Al ratio for Pd/BEA and Pd/SSZ-13 used as passive NO x adsorbers
KR101189238B1 (en) NOx Storage and Reduction Catalyst, Preparation Method thereof, and NOx Removing System Comprising the Same
Porta et al. Low temperature NOx adsorption study on Pd-promoted zeolites
Wang et al. Layered Pd/SSZ-13 with Cu/SSZ-13 as PNA− SCR dual-layer monolith catalyst for NOx abatement
CN112041051B (en) Hydrocarbon capture catalyst
Ryu et al. Ethylene trapping of palladium-impregnated zeolites for cold-start emission control
Li et al. Unraveling alkali-tolerance role of zeolite coupling CeWOx catalyst for NOx reduction
US11666886B2 (en) Hydrocarbon adsorption and desorption complex comprising zeolite with controlled cation ratio and preparation method therefor
Zelinsky et al. Pd/BEA hydrocarbon traps: Effect of hydrothermal aging on trapping properties and Pd speciation
JP2001293368A (en) Hydrocarbon adsorbent and method for adsorbing and removing hydrocarbon
JP4803487B2 (en) Nitrogen oxide selective reduction catalyst and method for producing the same
US20230173455A1 (en) Hydrocarbon adsorbent
US20250319453A1 (en) Hydrothermally stable hydrocarbon trap by controlling the composition ratio of cations within the beta zeolite and preparation method thereof
Ilmasani Mechanism of the passive NOx adsorption process on zeolite-supported Pd in controlling cold-start emissions
US12017202B2 (en) Hydrocarbon adsorption and desorption complex including gas adsorbing portion and reinforcing portion and method for preparing the same
Lin et al. Fighting hydrocarbon poisoning with alkali metal poisoning on Cu-SSZ-13 catalyst for NH3-SCR
Ilmasani Investigation of La promoted Pd/BEA Performance for Passive NOx adsorption processes
Mihai et al. The Effect of Si/Al Ratio for Pd/BEA and Pd/SSZ-13 Used as Passive NO
EP1565252A1 (en) Process for the treatment of waste gas and unit suitable for use therein

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200623

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HYUNDAI MOTOR COMPANY

Owner name: KOREA UNIVERSITY RESEARCH AND BUSINESS FOUNDATION

Owner name: KIA CORPORATION

A4 Supplementary search report drawn up and despatched

Effective date: 20211004

RIC1 Information provided on ipc code assigned before grant

Ipc: B01J 23/72 20060101ALI20210928BHEP

Ipc: B01J 29/72 20060101ALI20210928BHEP

Ipc: B01J 29/46 20060101ALI20210928BHEP

Ipc: B01J 29/40 20060101ALI20210928BHEP

Ipc: B01J 35/02 20060101ALI20210928BHEP

Ipc: B01J 35/10 20060101ALI20210928BHEP

Ipc: B01D 53/04 20060101ALI20210928BHEP

Ipc: B01J 20/34 20060101ALI20210928BHEP

Ipc: B01J 20/18 20060101ALI20210928BHEP

Ipc: B01J 20/28 20060101ALI20210928BHEP

Ipc: B01J 20/32 20060101AFI20210928BHEP

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230527

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20250219

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20250621